Demulsification compositions, systems and methods for demulsifying and separating aqueous emulsions

ABSTRACT

The present invention provides compositions, systems and methods for demulsifying an emulsion including an aqueous phase and an organic phase by adding an effective amount of a composition comprising at least one quaternary organopolysiloxane or salt thereof to the emulsion, the composition optionally including at least one of quaternary epihalohydrin/polyamine copolymers or salts, and/or (poly)diallyldimethylammonium halides.

This application is a division of U.S. patent application Ser. No.12/417,683, filed Apr. 3, 2009, which has now issued as U.S. Pat. No.8,268,975 and which is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

I. Field of the Invention

The present invention relates to compositions and systems comprisingquaternary organopolysiloxanes that can be useful for demulsifying andseparating aqueous emulsions and water-in-oil emulsions formed duringprocessing of organic materials such as bioproducts.

II. Technical Considerations

Bioprocesses can be used to produce a wide variety of bioproducts, suchas pharmaceuticals, insecticides, food additives, solvents, fuels, etc.Bioprocesses can utilize renewable feedstock sources such as corn,grain, algae, and other naturally occurring organic sources, and offerthe potential for an environmentally friendly and less costlyalternative to conventional synthesis routes that rely onpetroleum-based feedstocks. The ability to produce a valuable endproduct via a biological process, using microorganisms such as bacteria,fungi, mold, etc., is proving to be a promising approach for a growingnumber of derived products.

Bioproducts such as antibiotic pharmaceuticals (for example penicillin)or substances obtained from microorganisms such as bacteria, algae orfungi (for example spinosyns, streptomycin, erythromycin, efrotomycin,etc.), can be produced by fermentation of a culture of microorganismsand/or enzymes in a nutrient-rich media. The bioprocess produces abio-broth comprising a complex mixture of organic and inorganiccompounds such as the valuable bioproduct, the biomass of microorganismsor enzymes, unconverted nutrient medium, fats, proteins, carbohydrates,amino acids, water and surfactant. Thus, the desired bioproduct must beextracted from the undesirable components of the bio-broth.

The separation of the selective components from bio-broths is oftenperformed using liquid-liquid extractions. An extracting solvent,typically a water immiscible organic solvent such as amyl acetate,methyl ethyl ketone, methyl isobutyl ketone, amyl alcohol, butylalcohol, toluene, heptane or benzyl alcohol, is added to extract thedesired bioproduct from the aqueous phase to the organic phase, and thephases are separated. The broth components can form a stable emulsion asthe broth and solvent are mixed which is difficult to separate byphysical means, for example mechanical separation devices such assettlers, decanters and centrifuges. The resulting emulsion can occur asa dispersion of an organic phase within the aqueous phase, a dispersionof the aqueous phase within the organic phase, or both types ofdispersions can be present. The dispersed material, including organicssuch as microorganisms, enzymes, proteins, lipids and carbohydrates, canpossess a net negative charge or exhibit both polar and non-polarcharacteristics and be difficult to separate. These types of moleculescan form hydrogen bonds with polar solvents, such as the polar aqueousphase, while having non-polar regions which can be soluble in organicsolvent present in the less polar or non-polar organic phase. Thisresults in an emulsion which is relatively stable and difficult toseparate.

Nevertheless, depending on the components, some emulsions eventuallybreak by themselves, that is, such emulsions have only “temporarystability” and over time and with the aid of gravity or centrifugation,the emulsion separates into distinct layers. More commonly, ademulsifier is added to encourage or initiate separation by gravity orcentrifugation. Sodium chloride or another inorganic salt or an organicdemulsifier such as AKZO D5430 quaternary fatty acid amine (commerciallyavailable from Akzo Nobel Chemical, Inc.), or KR-L255alkylphenol-formaldehyde resin (commercially available from KroffChemical Co.) can be employed as a demulsifier.

Whether treated mechanically or chemically, upon separation, a solventphase and an aqueous phase are formed. Optionally, a solid phase can bepresent. The solvent phase can comprise the desired bioproduct, solventand small amounts of water and other impurities, such as organicmaterial, the structure of which may be similar to that of the desiredbioproduct and other undesirable components dissolved in the solvent.The aqueous phase can comprise the remaining components, including thebiomass of the microorganisms or enzymes, and there may be a smallamount of the desired bioproduct dissolved in the water and contained inthe biomass. Alternatively, the desired bioproduct can be present in theaqueous phase rather than in the solvent phase.

The solvent phase may be cleaned further after separation from theaqueous phase by performing additional extractions that can includeadjusting the process conditions, for example pH, temperature, or theaddition of other solvents to drive the equilibrium in the desireddirection to enhance the isolation of the desired bioproduct. If theaddition of water forms a secondary emulsion, separation may beaccomplished as described for the first emulsion. When the phasecontaining the desired bioproduct has been cleaned to the desired level,excess solvent or water, depending on the phase in which the bioproductis present, can be removed by evaporation.

Conventional methods for demulsification and separation of phases haveseveral drawbacks. For example, although inorganic salts such as sodiumchloride are routinely used as demulsifiers, the phase separation cantake place more slowly than desired, and the separation tends to involvea relatively large, indistinct interface, with poor segregation ofcomponents into the separate phases. For example, a significant portionof the desired bioproduct is often entrapped within cells of thebiomass. As a result, recovery of the bioproduct typically has beenfound to be as low as 80%.

Similar emulsions also may be encountered in other bioprocessingapplications, wastewater treatment or oil recovery. For example,emulsions can form during liquid extraction of plant materials (such asplant oils) from plant tissues. In crude oil production processes,water-in-oil emulsions can form in the presence of naturally occurringpolar surface-active molecules such as asphaltenes and resins; finesolids such as crystallized waxes, clays and scales; steam injection;and/or high shear conditions, for example at the wellhead in the chokevalve.

Use of conventional demulsifiers, such as alkylphenol-formaldehyderesins which contain phenol groups, can pose environmental concerns.Such systems are often formulated with aromatic solvents to improve theflow properties of the demulsifier, however, aromatic solvents such asbenzenes, xylenes, naphtha or napthalenes also can present environmentalconcerns. As environmental regulations become more stringent, there is aneed for more environmentally friendly or “green” demulsifiers whichquickly separate phases in emulsions, provide a well-defined interfaceto facilitate separation and that do not require centrifugation toseparate the phases of the emulsion.

SUMMARY OF THE INVENTION

In some non-limiting embodiments, the present invention providescompositions for demulsifying an emulsion comprising an aqueous phaseand an organic phase, the compositions comprising at least onequaternary organopolysiloxane or salt thereof in an amount effective toat least partially separate the aqueous phase from the organic phase.

In some non-limiting embodiments, the present invention providesdemulsification systems comprising: (a) an emulsion comprising anaqueous phase and an organic phase; and (b) a composition comprising atleast one quaternary organopolysiloxane or salt thereof in an amounteffective to at least partially separate the aqueous phase from theorganic phase.

In some non-limiting embodiments, the present invention provides methodsfor demulsifying an emulsion comprising an aqueous phase and an organicphase, comprising (a) adding an effective amount of a compositioncomprising at least one quaternary organopolysiloxane or salt thereof toan emulsion comprising an aqueous phase and an organic phase.

In some non-limiting embodiments, the present invention provides methodsfor demulsifying an emulsion produced in bioprocessing, comprisingadding an effective amount of a demulsifier to an emulsion thatcomprises at least one bioproduct which is desired to be extracted fromthe emulsion, the demulsifier comprising at least one quaternaryorganopolysiloxane or salt thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing summary, as well as the following detailed description,will be better understood when read in conjunction with the appendeddrawings. In the drawings:

FIG. 1 is a graph of phase separation as a function of total elapsedcentrifuging time for a S. Spinosa fermentation broth using di-isobutylketone as extraction solvent, and a demulsifying composition includinghexylene glycol carrier solvent and a quaternary organopolysiloxane saltaccording to the present invention compared to a similar demulsifyingcomposition without the cationic quaternary organopolysiloxane salt;

FIG. 2 is a graph of phase separation as a function of total elapsedcentrifuging time for a S. Spinosa fermentation broth using di-isobutylketone as extraction solvent, and a demulsifying composition includinghexylene glycol and/or water as a carrier solvent and a quaternaryorganopolysiloxane salt and a similar demulsifying composition includinga quaternary organopolysiloxane salt and a quaternaryepihalohydrin/polyamine copolymer, according to the present invention;and

FIG. 3 is a graph of phase separation at 1 minute elapsed centrifugingtime for a S. Spinosa fermentation broth using di-isobutyl ketone asextraction solvent, and demulsifying compositions including a solventmixture of hexylene glycol and water and a varying ratio of quaternaryorganopolysiloxane salt to quaternary epihalohydrin/polyamine copolymer,as described in Table 3, according to the present invention.

DETAILED DESCRIPTION

For the purposes of this specification, unless otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions,dimensions, physical characteristics, and so forth, used in thespecification and claims are to be understood as being modified in allinstances by the term “about”. Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the followingspecification and attached claims are approximations that may varydepending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical values, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include any and all sub-ranges betweenand including the recited minimum value of 1 and the recited maximumvalue of 10, that is, all sub-ranges beginning with a minimum valueequal to or greater than 1 and ending with a maximum value equal to orless than 10, and all sub-ranges in between, e.g., 1 to 6.3, or 5.5 to10, or 2.7 to 6.1.

As used herein, “alkyl” means an aliphatic hydrocarbon group which maybe straight or branched and comprising about 1 to about 20 carbon atomsin the chain. Non-limiting examples of suitable alkyl groups containabout 1 to about 18 carbon atoms in the chain, or about 1 to about 6carbon atoms in the chain. “Branched” means that one or more lower alkylgroups such as methyl, ethyl or propyl, are attached to a linear alkylchain. “Lower alkyl” or “short chain alkyl” means a group having about 1to about 6 carbon atoms in the chain which may be straight or branched.Non-limiting examples of suitable alkyl groups include methyl, ethyl,n-propyl, isopropyl and t-butyl.

“Alkylene” means a difunctional group obtained by removal of a hydrogenatom from an alkyl group that is defined above. Non-limiting examples ofalkylene include methylene, ethylene and propylene.

“Aryl” means an aromatic monocyclic or multicyclic ring systemcomprising about 6 to about 14 carbon atoms, or about 6 to about 10carbon atoms. Non-limiting examples of suitable aryl groups includephenyl and naphthyl.

“Heteroaryl” means an aromatic monocyclic or multicyclic ring systemcomprising about 5 to about 14 ring atoms, or about 5 to about 10 ringatoms, in which one or more of the ring atoms is an element other thancarbon, for example nitrogen, oxygen or sulfur, alone or in combination.Non-limiting examples of suitable heteroaryls include pyridyl,pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone, isoxazolyl,isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl,pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl,quinoxalinyl, phthalazinyl, oxindolyl, imidazo[1,2-a]pyridinyl,imidazo[2,1-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl,benzimidazolyl, benzothienyl, quinolinyl, imidazolyl, thienopyridyl,quinazolinyl, thienopyrimidyl, pyrrolopyridyl, imidazopyridyl,isoquinolinyl, benzoazaindolyl, 1,2,4-triazinyl, benzothiazolyl and thelike. The term “heteroaryl” also refers to partially saturatedheteroaryl moieties such as, for example, tetrahydroisoquinolyl,tetrahydroquinolyl and the like.

“Halogen” or “halo” means fluorine, chlorine, bromine, or iodine. Insome non-limiting embodiments, the halogen groups are fluorine, chlorineor bromine.

It should also be noted that any carbon, as well as heteroatom, withunsatisfied valences in the text, schemes, examples and Table herein isassumed to have the sufficient number of hydrogen atom(s) to satisfy thevalences.

When any variable (e.g., aryl, heterocycle, R², etc.) occurs more thanone time in any constituent, its definition on each occurrence isindependent of its definition at every other occurrence.

As used herein, the term “composition” is intended to encompass aproduct comprising the specified ingredients in the specified amounts,as well as any product which results, directly or indirectly, from thecombination of the specified ingredients in the specified amounts.

As used herein, “formed from” or “prepared from” denotes open, e.g.,“comprising”, claim language. As such, it is intended that a composition“formed from” or “prepared from” a list of recited components be acomposition comprising at least these recited components or the reactionproduct of at least these recited components, and can further compriseother, non-recited components, during the composition's formation orpreparation.

As used herein, the term “polymer” means a substance, typically of largemolecular mass, comprising structural units or monomers. Examples ofpolymers include oligomers, homopolymers and copolymers. The term“oligomer” means a polymer consisting of only a few monomer units up toabout ten monomer units, for example a dimer, trimer or tetramer.

As used herein, “bioproduct” means a product prepared from, inter alia,an organic material. Non-limiting examples of bioproducts includepharmaceuticals, insecticides, food additives, solvents, fuels, etc. Insome non-limiting embodiments, bioproducts can be produced by abiological process (bioprocess), using microorganisms such as bacteria,fungi, mold, etc. Bioprocesses can utilize renewable feedstock sourcessuch as corn, grain, algae, and other naturally occurring organicsources.

The compositions and methods of the present invention can be useful in awide variety of emulsion separation applications, non-limiting examplesof which include bioprocessing applications such as separatingbioproducts from an expended nutriment medium; preparation of organicmaterials such as ethanol, lactic acid, acetic acid, butanol, citricacid, glucose, and fructose; separating plant oils (such as soybean oil)from plant media or aqueous biomass; vitamin production; crude oil andnatural gas production; oil reprocessing for fuel feedstock; fat, oiland grease (FOG) removal in wastewater applications; and oily wastetreatment in steel mill, foundry and metal working applications.

As used herein, “emulsion” means an intimate mixture comprising two ormore liquid phases, such as oil and water, wherein the liquids aremutually insoluble and where either phase may be dispersed in the other.Optionally, a solid phase can be present. A bioproduct emulsion cancomprise, for example, one or more bioproducts, microorganisms, enzymes,proteins, lipids, vitamins, carbohydrates, fats, amino acids or mixturesthereof, present in two or more liquid phases. The individual componentsof the bioproduct emulsion can be present independently in one or moreof the liquid phases.

A stable oil-in-water emulsion is a colloidal system of electricallycharged oil droplets surrounded by an ionic environment. For example, inan oily waste emulsion in which oil is dispersed in a water phase, theoils can be any hydrocarbon or organic fluid, such as waste oil,lubricants, cutting fluids, heavy hydrocarbons such as tars, grease,crude oils, diesel oils, and light hydrocarbons such as gasoline,kerosene and jet fuel. The concentration of oils in the wastewater canrange from a few ppm up to about 10 weight percent by volume or more.

Emulsions can be broken by chemical, physical or electrolytic means. Thebreaking of an emulsion to separate the components is referred to asdemulsification or resolution. As used herein, “demulsifying” or“demulsification” means separating two or more components of anemulsion, such as separating an organic or oil phase from an aqueous orwater phase. To break or separate an emulsion, the factors thatstabilize the emulsion must be disrupted to allow the emulsifieddroplets to coalesce. The accumulated electric charges on the emulsifieddroplet can be neutralized by introducing a charge opposite to that ofthe droplet. The compositions of the present invention include cationiccomponents which are capable of neutralizing negatively chargedcomponents of the emulsion, for example organic components such asmicroorganisms or organic matter.

While not intending to be bound by any theory, the treatment ofemulsions according to the methods of the present invention is believedto comprise several steps: (1) orientation of the demulsifier at thewater/solvent interface; (2) partial or complete neutralization ofcharged component(s) that stabilize the emulsion; (3) interference withthe emulsifying properties of surface active agent(s) or othercomponent(s) of the emulsion; and (4) rapid resolution of at least twodistinct phases that are separable, for example by centrifugation,filtration or gravity.

The compositions of the present invention comprise at least one (one ormore) cationic quaternary organopolysiloxanes and salts thereof. In somenon-limiting embodiments, the quaternary organopolysiloxanes and saltsare at least partially water soluble. As used herein with respect to thequaternary organopolysiloxanes and salts, “water soluble” means that thequaternary organopolysiloxane is capable of being at least partially orfully dissolved in water at ambient temperature (about 25° C.). Thesolubility of a component of the compositions of the present invention,for example solubility of the quaternary organopolysiloxane, can bedetermined by adding 1.0 weight percent of the component to water at 25°C. and mixing thoroughly (about 5 minutes) with a magnetic stirrer. Themixture is permitted to stand for 24 hours and the clarity andseparation of components of the mixture is assessed by visualobservation. A clear, generally haze-free solution is “water soluble”, ahazy/turbid solution is “water dispersible” or “partially watersoluble”, and a mixture that separates into layers or has noticeablesolid particulates is “water insoluble”. The evaluation can be performedin the presence of up to 1.0 weight percent of a cosolvent, such asisopropyl alcohol, to aid in solubilization of the component.Alternatively, the same procedure can be performed using an organicsolvent, such as toluene, instead of water to evaluate the component forlipophile solubility.

In some non-limiting embodiments, suitable quaternaryorganopolysiloxanes and salts thereof for use in the compositions andmethods of the present invention, include those represented by thefollowing Formulae (I) and (II):(R—O)—CH₂CH(OH)CH₂—R′  (I)(R—O)—C(O)CH₂—R′  (II)wherein

-   R is

wherein A is selected from the group consisting of:

-   a bond, —(CH₂CH₂O)_(x)—, —(CH₂CH(CH₃)O)_(y)—, and combinations    thereof;

a is an integer from 0 to 200;

b is an integer from 0 to 200;

c is an integer from 1 to 200 or 1 to 100;

each R¹, if present, is selected from —(CH₂)_(n)CH₃ and phenyl wherein nis an integer from 0 to 32 or 0 to 10;

each R², if present, is—(CH₂)₃—(OCH₂CH₂)_(n)—(OCH₂CH(CH₃))_(y)—(OCH₂CH₂)_(z)—OH;

-   R′ is selected from:

wherein R³, R⁴, and R⁵ are each independently alkyl having from 1 to 22carbon atoms, or 1 to 20 carbon atoms, and X is an ion selected from thegroup consisting of Cl, Br, CH₃SO₄ and CH₃CH₂SO₄;

wherein R⁶ is alkyl having from 6 to 22 carbon atoms, or 6 to 20 carbonatoms; R⁷ and R⁸ are independently selected from the group consisting ofmethyl and ethyl; and n is an integer from 1 to 5, and X is an ionselected from the group consisting of Cl, Br, CH₃SO₄ and CH₃CH₂SO₄; and

wherein R⁹ is alkyl having from 6 to 22 carbon atoms, or 6 to 20 carbonatoms; and v is an integer from 1 to 5, and X is an ion selected fromthe group consisting of Cl, Br, CH₃SO₄ and CH₃CH₂SO₄; and

-   each x, y and z is an independently selected integer each ranging    from 0 to 22, or 0 to 20, and in some embodiments the sum of x, y    and z is at least 1.

In some non-limiting embodiments, X⁻ is Cl⁻.

In some non-limiting embodiments, R is

wherein x, y and z are integers and are each independently selected from0 to 20, and a, b, c, R¹ and R² are as set forth above.

Non-limiting examples of polymers of Formulae (I) and (II) and methodsfor making the polymers are disclosed in U.S. Pat. Nos. 5,098,979 and5,153,294, each incorporated by reference herein. The polymers ofFormulae (I) and (II) can be prepared by reaction of a hydroxylcontaining silicone polymer with a suitable halohydrin (such asepichlorohydrin or epibromohydrin) or halo acid (such as chloraceticacid). One method of preparing the reactive hydroxyl containing siliconepolymer is to react silanic hydrogen containing polymer with allylalcohol or allyl alcohol alkoxylate monomer in a manner well known tothose skilled in the art, for example as is disclosed in U.S. Pat. No.4,083,856. In some embodiments, the hydroxy containing silicone polymercan be alkoxylated with ethylene oxide, propylene oxide or mixturesthereof. The type of alkylene oxide and amount present in the siliconepolymer results in a series of products ranging in water/oil solubility.

In some non-limiting embodiments, suitable quaternaryorganopolysiloxanes and salts thereof for use in the compositions andmethods of the present invention include those represented by Formula(III):

wherein a, b, c, R¹ and R² are each as set forth above, b is at least 1,and R is an alkyl group having 1 to 24 carbon atoms, or 1 to 6 carbonatoms.

In some non-limiting embodiments, suitable quaternaryorganopolysiloxanes and salts thereof of Formula (III) include thoserepresented by the following Formula (IIIa):

wherein a, b and R are as discussed above for Formula (III).

In some non-limiting embodiments, suitable quaternaryorganopolysiloxanes and salts thereof for use in the compositions andmethods of the present invention include those represented by thefollowing Formula (IV):

wherein a is an integer from 0 to 200; and A and R′ are as set forthabove.

In some non-limiting embodiments, suitable quaternaryorganopolysiloxanes and salts thereof of Formula (IV) include thoserepresented by the following Formula (IVa):

wherein a is an integer from 0 to 200 and R is an alkyl group having 1to 24 carbon atoms, or 1 to 6 carbon atoms.

Non-limiting examples of quaternary organopolysiloxanes and salts ofFormulae (III) and (IV) include KR-DP0319, KR-DP0320, KR-DP0324,KR-DP0325, and KR-DP0470 water soluble quaternary organopolysiloxanes insolvent; and KR-DP0326, KR-DP0460, and KR-DP0471 water insolublequaternary organopolysiloxanes in solvent, commercially available fromKroff Chemical Co., Inc. of Pittsburgh, Pa.

In some non-limiting embodiments, suitable quaternaryorganopolysiloxanes and salts can be represented by Formula (V) (alsoreferred to as silicone polyether fatty quats):

wherein R is an alkyl group having from 4 to 22 carbon atoms. In someembodiments, R can be the residue of a fatty acid group, such as analkyl group having from 4 to 22 carbon atoms, or 4 to 20 carbon atoms,or 4 to 18 carbon atoms, or 4 to 12 carbon atoms.

Non-limiting examples of suitable quaternary organopolysiloxanes andsalts of Formula (V) include KR-DP0327 and KR-DP-0453 water solublecationic quaternary polyether fatty amide organopolysiloxanes insolvent, commercially available from Kroff Chemical Co. The compoundscontain a fatty portion which is derived from a fatty amine.Incorporation of this type of group into the silicone molecule resultsin increased solubility in many organic solvents. The fatty portion ofthe amine can be derived from any fatty acid, for example having from 4to 24 carbon atoms such as stearic acid or oleic acid.

In some non-limiting embodiments, the quaternary organopolysiloxane(s)or salt(s) comprises up to about 100 weight percent of the composition,or about 5 to about 100 weight percent, or about 10 to about 30 weightpercent or about 20 weight percent based upon the weight of (1)quaternary organopolysiloxane or salt and (2) quaternaryepihalohydrin/polyamine copolymer (if present), and/or p(DADMAC) (ifpresent) in the composition (e.g., not including solvent or carrier suchas water).

In some embodiments, such as the Kroff products discussed above, thequaternary organopolysiloxane or salt thereof is present with at leastone solvent. Non-limiting examples of suitable solvents include glycolssuch as ethylene glycol, propylene glycol, hexylene glycol, diethyleneglycol, polyglycols such as polyethylene glycol and polypropyleneglycol, polyols such as glycerol (glycerine) and short chain aliphaticalcohols such as methanol, ethanol and isopropyl alcohol, and mixturesthereof. The amount of solvent can range from about 10 to about 100weight percent, or about 55 to about 90 weight percent, or about 70 toabout 75 weight percent, based upon total weight of theorganopolysiloxane and solvent. Quaternary polysiloxanes tend to be veryviscous and generally require a solvent to improve their handlingproperties. In general, it is commercially desirable to limit thesolvent content to a minimum that will provide the desired viscosityproperty of the product.

In some non-limiting embodiments, the compositions of the presentinvention comprise at least one cationic quaternaryepihalohydrin/polyamine polymer or salt thereof. Suitableepihalohydrin/polyamine polymers can be prepared by the polymerizationof at least one epihalohydrin, at least one alkylene diamine and atleast one alkylene polyamine in which at least some of the nitrogenatoms of the copolymer have been quaternized. The quaternaryepihalohydrin/polyamine polymer comprises or consists essentially of thefollowing repeating units:

wherein R and R² are each independently selected from alkyl groupshaving 1 to 3 carbon atoms; E is the residue obtained after bifunctionalreaction of a compound selected from the group consisting ofepihalohydrins (such as epichlorohydrin or epibromohydrin), diepoxides(such as 1,4-butanediol-diglycidyl ether), precursors thereof andmixtures thereof; and A is the residue obtained after reaction of apolyfunctional polyamine selected from the group consisting of ammonia,primary amines, alkylene diamines of 2 to 6 carbon atoms,polyalkylpolyamines of the structure:

wherein y represents an integer of about 1 to 5, R₃ is an alkyleneradical of about 2 to 6 carbon atoms, and R₄ is selected from the groupconsisting of hydrogen, alkyl of about 1 to 3 carbon atoms, andco-aminoalkyls of about 2 to 6 carbon atoms, a polyglycolamine, forexample having the structure:

wherein x is an integer of about 1 to 5; piperazine heteroaryl diaminesor aryl diamines.

X⁻ is an ion forming the anionic portion of the polyquaternary compound,m to p are integers which represent the molar quantities of aminereactants, the ratio of m to p being from 99:1 to 85:15; n representsthe molar quantity of E forming the principal chain of thepolyquaternary, the molar quantity represented by n being substantiallyequal to the sum of the molar quantities of m and p; the polyfunctionalamine containing, in addition to the amount of E required fordifunctional reaction therewith, an amount of E which is from zero toabout the full functional equivalency remaining in A, the sum of m, nand p being such as to provide a polyquaternary compound which as a 37%aqueous solution, by weight, based on the total weight of the cationicportion of the polyquaternary compound has a viscosity at 25° C. of atleast 10 centistokes; and z is an integer such as to satisfy anionrequirements of the polyquaternary compound. Non-limiting examples ofsuch quaternary epihalohydrin/polyamine polymers and processes formaking the same are set forth in U.S. Pat. No. 3,738,945, incorporatedby reference herein.

In some non-limiting embodiments, the quaternary epihalohydrin/polyaminepolymer and salts thereof are condensation polymerization reactionproducts having a branched structure comprising or consistingessentially of the following repeating units:

wherein each of R¹, R², R³ and R⁴ are independently selected fromhydrogen or

and wherein x ranges from about 50 to about 200, y ranges from 0 toabout 10 and z ranges from about 50 to about 200.

In some embodiments, suitable quaternary epihalohydrin/polyaminepolymers and salts thereof include liquid quaternaryepihalohydrin/polyamine polymer solutions in water, such as those havingC.A.S. Registry No. 42751-79-1. Non-limiting examples of liquidquaternary epihalohydrin/polyamine polymer solutions in water includefor example KR-C1620, KR-C1630, KR-C1650 and KR-C1680 liquid polyaminesolutions, commercially available from Kroff Chemical Co. In otherembodiments, the quaternary epihalohydrin/polyamine polymer can have theC.A.S. Registry No. 25988-97-0.

In some embodiments, it is preferred that the quaternaryepihalohydrin/polyamine polymer be NSF and/or GRAS approved for use inproducts for consumption by or application to humans. GRAS standards forsuch materials are set forth in §21 C.F.R. 570.30-570.35. The quaternaryepihalohydrin/polyamine polymer can be present in a carrier or diluent,such as water. The amount of carrier can range from about 40 to about 70weight percent, or about 45 to about 55 weight percent, or about 50weight percent, based upon total weight of the quaternaryepihalohydrin/polyamine polymer and carrier.

In some embodiments, the quaternary epihalohydrin/polyamine polymershave a weight average molecular weight of less than about 2,000,000grams/mole, or less than about 1,000,000 grams/mole, or about 20,000 toabout 300,000 grams/mole.

In some embodiments, the quaternary epihalohydrin/polyamine copolymercomprises up to about 95 weight percent of the composition, or about 5to about 95 weight percent, or about 70 to about 90 weight percent orabout 80 weight percent based upon the weight of (1) quaternaryorganopolysiloxanes and (2) quaternary epihalohydrin/polyaminecopolymers, and/or p(DADMAC) (if present) in the composition (e.g., notincluding solvent or carrier such as water).

In some non-limiting embodiments, the compositions of the presentinvention comprise one or more (poly)diallyldimethylammonium halidessuch as diallyldimethylammonium chloride polymer (known as “p(DADMAC)”,“p(DMDAAC)” or “p(DADM)”). Methods for preparing p(DADMAC)s aredisclosed in U.S. Pat. Nos. 4,092,467 and 4,151,202, each incorporatedby reference herein. Poly-dialkyldiallyl ammonium chloride, which is apolymer of dialkyldiallyl ammonium chloride and may be writtenpoly-(dialkyldiallyl ammonium chloride), typically has a molecularweight of from about 10,000 to about 2,000,000 or more, and is discussedin U.S. Pat. No. 3,782,546, incorporated by reference herein.Commercially available dimethyldiallyl ammonium chloride andpolydimethyldiallyl ammonium chloride generally contain a mixture ofmono and diallyl forms. Poly-dialkyldiallyl ammonium salts may beprepared by any of a number of known techniques. U.S. Pat. No. 3,782,546identifies several U.S. patents which discuss the preparation and use ofpoly-dialkyldiallyl ammonium chlorides. Non-limiting examples ofsuitable p(DADMAC)s include KR-C2320, KR-C2370, KR-C2553, KR-C2570 andKR-C2623, available from Kroff Chemical Co.

In some embodiments, the p(DADMAC) comprises up to about 95 weightpercent of the composition, or about 5 to about 95 weight percent, orabout 70 to about 90 weight percent or about 80 weight percent basedupon the weight of (1) quaternary organopolysiloxanes or salts and (2)quaternary epihalohydrin/polyamine copolymers or salts (if present),and/or p(DADMAC) in the composition (e.g., not including solvent orcarrier such as water).

The degree of quaternization of the quaternary organopolysiloxane,quaternary epihalohydrin/polyamine copolymer, and/or p(DADMAC) can befrom about 25% to about 100%, or about 70% to about 90%, or about 75%,based on the number of nitrogen atoms quaternized. Thus, some or all ofthe nitrogen atoms of the above compounds or polymers may bequaternized. The quaternization product may be used directly as ademulsifier for resolving emulsions produced in preparation ofpharmaceuticals by fermentation or in diluted form, such as an aqueoussolution, for demulsification. Alternatively, the conjugate acid saltsthereof may be used directly or in similar diluted form. Such salts maybe formed by addition of an acid, such as hydrochloric acid, to thequaternized oxyalkylated amine.

The composition comprises quaternary organopolysiloxane(s) or salt(s),and in some embodiments can further comprise one or more of quaternaryepihalohydrin/polyamine copolymer(s) or salt(s), and/or p(DADMAC). Thequaternary organopolysiloxane(s) or salt(s), quaternaryepihalohydrin/polyamine copolymer(s) or salt(s), and/or p(DADMAC) can bepremixed prior to mixing with the emulsion, or added separately orsequentially in any order desired.

In some embodiments, other additives can be included in compositions ofthe present invention. Non-limiting examples of such additives includeother demulsifiers that are chemically different from the demulsifiersdiscussed above (for example having at least one different atom ordifferent molecular arrangement), surfactants or wetting agents such asnonionic or cationic surfactants, nonionic polysiloxanes,compatibilizers and coupling agents. Non-limiting examples of suitableadditives include fatty amines such as ARMEEN® fatty amines commerciallyavailable from Akzo Nobel Surfactants, fatty amine polyglycol ethers,quaternary ammonium salts, oxyalkylated phenolic resins, alkoxylatedalkylphenol formaldehyde resins, ethylene oxide/propylene oxidecopolymers, polyoxyalkylene glycols, polyalkylene glycols, siliconepolyethers, nonionic polysiloxanes such as Dow DM-2 polydimethylsiloxaneor mixtures thereof. Non-limiting examples of suitable compatibilizersinclude low molecular weight alcohols such as butyl carbitol andphosphate esters.

Such additives can be present in an amount such that the additivecomprises less than about 30 percent by weight, or less than about 15percent by weight, or less than about 5 percent by weight, or less thanabout 3 percent by weight, based on the total weight of the composition.In some non-limiting embodiments, the aforementioned optional additivescan be pre-mixed with the quaternary organopolysiloxane (and quaternaryepihalohydrin/polyamine copolymer(s) or salt(s), and/or p(DADMAC)), ifpresent, before being added to the emulsion, or the components can beadded simultaneously or sequentially in any order desired.

The compositions of the present invention can be useful as demulsifiersin resolving emulsions. Non-limiting examples of such emulsions includethose produced in preparation of bioproducts such an antibiotics, forexample, penicillin or substances obtained from fungus (spinosads,streptomycin, erythromycin, efrotomycin, etc.), by fermentation in whicha culture of microorganisms or enzymes in a nutriment medium, such asvegetable oil in a water base, ferments to produce a desired bioproduct.The emulsion can comprise one or more bioproducts, microorganisms,enzymes, proteins, lipids, vitamins, carbohydrates, fats, amino acids,organic solvents, emulsifiers, nutrient from the nutriment medium,particulate matter including enzymes or microorganisms, and variousorganic or inorganic compounds such as electrolytes, trace mineralsand/or buffering agents. Such emulsions are produced in a broad range ofpHs and the components are present in a variety of relative proportions.

In some embodiments, the emulsion can comprise fermentation productssuch as A83543 family of compounds, referred to as spinosyns, that areproduced by certain strains of Saccharopolyspora spinosa. The previouslydisclosed naturally produced spinosyns have a 5,6,5-tricylic ringsystem, fused to a 12-membered macrocyclic lactone, a neutral sugar(rhamnose) and an amino sugar (forosamine). The known spinosyns havebeen referred to as factors or components, and each has been given anidentifying letter designation, i.e., spinosyn A, B, etc. The compoundsare useful for the control of arachnids, nematodes and insects, inparticular Lepidoptera and Diptera species, are environmentally friendlyand have a good toxicological profile. U.S. Pat. No. 5,362,634 disclosesspinosyns A, B, C, D, E, F, G, H, and J. WO 93/09126 discloses spinosynsL, M, N, Q, R, S, and T. WO 94/20518 discloses spinosyns K, O, P, U, V,W, and Y, and derivatives thereof. Other spinosyn compounds includethose disclosed in WO 97/00265, and U.S. Pat. No. 6,455,504(Saccharopolyspora species designated LW107129 (NRRL 30141)). Each ofthese U.S. patents and PCT WO publications is incorporated by referenceherein.

Spinosyns are fermentation products produced by chemical mutants ofactinomycetes soil bacterium Saccharopolyspora spinosa. The bacteriumcan be grown aerobically in an aqueous growth medium to producebiologically active metabolites called spinosyns. The aqueous growthmedium can contain components such as proteins, carbohydrates, oils, andminerals, for example corn solids, cottonseed flour, soybean flour,glucose, methyl oleate and calcium carbonate. “Spinosad Crops”, NationalOrganic Standards Board Technical Advisory Panel Review (Apr. 4, 2002),incorporated by reference herein. The spinosad fraction (about 85%spinosyn A and 15% spinosyn D) is soluble in organic solvents such asmethanol and can be extracted from the biomass by centrifugation orfiltering to remove solids, concentration by evaporation, conversion tosalt by mixing with acidified water, and crystallized from the water byadding base to neutralize the solution. Spinosad Crops at page 1.

Similar emulsions, which also can be treated with the demulsifiers ofthis invention, may be the result of other bioprocessing applications,wastewater treatment, and oil recovery. Wastewater treatment can involveseparating waste oil, lubricants and/or greases from industrial oilywastewater which include oil, dispersed solids and emulsified water,such as are produced in chemical processing, steel and aluminumindustries, automotive industry, cotton and wool manufacturingprocesses, laundry industry and the refinery industry. Emulsified oil inwastewater is typically present in amounts of about several hundred totens of thousands of ppm or more. The United States EnvironmentalProtection Agency (EPA) and local governments have placed limits on theamount of oil and grease in water to be discharged into public drinkingwater supplies or waterways.

The compositions of the present invention can be environmentallydesirable compared to conventional demulsifiers, such asalkylphenol-formaldehyde resins which can contain phenols.

The demulsifiers of the present invention can be remarkably fast acting,with application of a very small amount of the demulsifier producing anearly immediate phase separation with an exceptionally clear,well-defined interface, and almost all of the desired product orbioproduct segregated into one distinct phase. As used herein,“interface level” means the surface between two immiscible phasesdetermined by visual observation, as evidenced by different physicalproperties between the phases, for example different colors, differentopacity, different turbidity, and/or different densities between thephases. The interface level can be determined by stirring an emulsionincluding demulsifier for about 5 minutes with a magnetic stirrer, thenhomogenizing using a high shear Turran mixer until a stable emulsion isformed. The emulsion is then stirred for about 15 minutes to verify thestability of the emulsion. A 10 ml sample of homogenized emulsion isplaced in a conventional 15 ml conical centrifuge tube, placed in acentrifuge and spun down, generally for up to about 5 minutes at 3100rpm. An example of a suitable centrifuge is an IEC Centra CL2 centrifugewhich is available from Thermo Fisher Scientific, Inc. The measuredphase separation results are normalized to a starting value of 10 ml andcompared to the phase separations measured using the same process andbio-broth, but without the addition of the demulsifying agent. Theinterface level is measured as the visual boundary between the top layer(generally the solvent layer) and any material below the top layer (suchas water, solids, and any unseparated solvent/water (rag layer)).

The amount of demulsifier used to treat the emulsion is an amounteffective to at least partially separate an aqueous phase of theemulsion from an organic phase of the emulsion, and in some non-limitingembodiments can range from about 1 to about 200,000 ppm or more, orabout 10 to about 50,000 ppm, or about 50 to about 50,000 ppm, or about100 to about 20,000 ppm, or about 100 to about 10,000 ppm, or about 500to about 10,000 ppm, or about 1,000 to about 5,000 ppm based upon theamount of emulsion to be treated. In some non-limiting embodiments, theamount of demulsifier can range from about 1 to about 200,000 or moremicroliters (μl) per liter of emulsion to be treated, or about 10 toabout 50,000 μl/l, or about 50 to about 50,000 μl/l, or about 100 toabout 20,000 μl/l, or about 100 to about 10,000 μl/l, or about 500 toabout 10,000 μl/l, or about 1,000 to about 5,000 μl/l. The optimalproportion depends on the particular emulsion being treated. Suchemulsions typically comprise about 2% by weight to about 75% by weight,often about 50% by weight water. Typically, some such emulsions havefirst been neutralized to a pH of from about 7 to about 7.4. However,other emulsions have other pHs, and it has been found that thedemulsifiers of this invention are applicable over a wide pH range—atleast from about 3 to about 11. If desired, the demulsifier may be mixedinto the emulsion by shaking or stirring.

More specifically, upon application of a demulsifier of this inventionto such emulsions, the emulsion usually separates immediately intodistinct phases with a sharp, well-defined interface, and particulatematter in the emulsion being treated is sequestered into the aqueousphase. The phase separation can be essentially complete, with little orno residual emulsion remaining. Where the desired pharmaceutical orcomponent resides is dependent on where and how the manufacturermanipulates the pH. For example, pH adjustment may cause the desiredcomponent to collect in the water phase, while a different pH adjustmentmay cause the desired component to collect in the organic phase.

In some non-limiting embodiments, the compositions and methods of thepresent invention can be used to separate bioproducts orpharmaceuticals, such as penicillin, from fermentation products orbio-broths.

In other non-limiting embodiments, the compositions and methods of thepresent invention can be used to separate plant oils which are dispersedin an aqueous biomass.

In some non-limiting embodiments, the compositions of the presentinvention can be used as demulsifiers in an effective amount to reduceor eliminate the need for centrifugation, which can significantly reduceprocessing, equipment costs and processing time. An effective amount toeliminate centrifugation can be about 25% to about 50% more than theamounts required for centrifugation, and can be the amounts of about 1to about 200,000 ppm or more listed above, based upon the amount ofemulsion to be treated.

The compositions of the present invention can include carrier solventssuch as water, hexylene glycol, propylene glycol and isopropyl alcohol,which are more environmentally friendly and less volatile than carriersolvents typically used for commercially available demulsifiers, such asbenzene, diethyl benzene, trimethyl benzene, xylenes, naphtha ornaphthalenes.

In some non-limiting embodiments, the present invention provides methodsfor demulsifying an emulsion comprising an aqueous phase and an organicphase, comprising (a) adding an effective amount of a compositioncomprising at least one cationic quaternary organopolysiloxane or saltthereof, optionally with at least one quaternary epihalohydrin/polyaminecopolymer, or optionally with at least one polydimethyldiallyl ammoniumchloride polymer, to an emulsion comprising an aqueous phase and anorganic phase. The aqueous phase and organic phase can be separated asdiscussed above, for example by gravity, centrifugation, etc.

In some embodiments, the present invention provides methods fordemulsifying an emulsion produced in bioprocessing, comprising adding aneffective amount of a demulsifier to an emulsion that comprises at leastone bioproduct which is desired to be extracted from the emulsion, thedemulsifier comprising at least one quaternary organopolysiloxane orsalt thereof, optionally with at least one quaternaryepihalohydrin/polyamine copolymer, and/or optionally with at least onepolydimethyldiallyl ammonium chloride polymer as discussed above.

The invention will be further described by reference to the followingexamples. Unless otherwise indicated, all parts and percentages are byweight.

EXAMPLES Example 1

The phase separation of an emulsion including S. Spinosa fermentationbroth with di-isobutyl ketone as extraction solvent was evaluated usingdemulsifying compositions of the present invention including either acationic quaternary organopolysiloxane salt or a mixture of the cationicquaternary organopolysiloxane salt with a quaternaryepihalohydrin/polyamine copolymer. Hexylene glycol, water and blendsthereof were used as the carrier solvent for the demulsifyingcomposition. The fermentation broths used in the examples belowcomprised various proteins from natural sources, carbohydrates, lipids,trace minerals and/or electrolytes for pH buffering.

The fermentation broth was adjusted with ammonium hydroxide to analkaline value of approximately pH 9.8. The pH-adjusted fermentationbroth was mixed with di-isobutyl ketone solvent at a ratio of 2 partsbio-broth to 3 parts solvent. To this mixture, a predetermined amount ofa demulsifying composition of the present invention including either aquaternary organopolysiloxane salt or a mixture of a quaternaryorganopolysiloxane salt with a quaternary epihalohydrin/polyaminecopolymer was added. For comparison, a Control composition was preparedusing the same components as the demulsifying composition, exceptwithout the quaternary organopolysiloxane salt and quaternaryepihalohydrin/polyamine copolymer. The components of each demulsifiercomposition are set forth in Table 1 and Table 2 below.

TABLE 1 Solvent Product Demulsifier (weight %) (weight %) KR-DP0320 70%quaternary organopolysiloxane salt, 30% Hexylene molecular weight ~26000Glycol KR-DP0356 70% quaternary organopolysiloxane salt, 30% Propylenemolecular weight ~2600 Glycol KR-DP0319 70% quaternaryorganopolysiloxane salt, 30% Hexylene molecular weight ~500 GlycolKR-DP0324 70% quaternary organopolysiloxane salt, 30% Hexylene molecularweight ~4300 Glycol KR-C1630 50% quaternary epihalohydrin/polyamine 50%Water copolymer, molecular weight ~33,000 KR-C2570 40%polydimethyldiallyl ammonium 60% Water chloride, molecular weight~250,000

TABLE 2 Composition # (wt. %) Component #1 (wt. %) Component #2 1 100KR-DP0320 0 2 100 KR-C1630 0 3 100 KR-C2570 0 4 75 KR-DP0320 25 KR-C16305 50 KR-DP0320 50 KR-C1630 6 25 KR-DP0320 75 KR-C1630 7 50 KR-DP0320 50KR-C2570

The resulting mixture was stirred with a magnetic stirrer forapproximately 5 minutes. The mixture was then homogenized using a highshear Turrax mixer until a stable emulsion was formed. This emulsion wasthen stirred for approximately 15 minutes to verify the stability of theemulsion.

A 10 ml sample of each emulsion was taken and placed into a conventional15 ml conical centrifuge tube and spun down in a centrifuge at 3100 rpm,measuring the phase separation at pre-determined time intervals. Thecentrifuge was an IEC Centra CL2 centrifuge available from Thermo FisherScientific, Inc. For the intent of these Examples, 5 minutes representedthe maximum practical time for centrifugation; phase separation isessentially completed for the test condition and minimal further phaseseparation is anticipated beyond 5 minutes. The measured phaseseparation results were than normalized to a starting value of 10 ml andcompared to the phase separations measured using the same process andfermentation broth, but without the addition of the de-emulsifyingagent. This comparison was made to show that the quaternaryorganopolysiloxane salt and quaternary epihalohydrin polyamine copolymerenhanced the phase separation rate. This experiment was repeatednumerous times using different production runs of the fermentation brothand varying dosage levels of the cationic siloxane.

FIG. 1 is a graph of phase separation as a function of total elapsedcentrifuging time for a S. Spinosa fermentation broth using di-isobutylketone as extraction solvent, and a demulsifying composition(Composition #1) according to the present invention compared to asimilar demulsifying composition without the quaternaryorganopolysiloxane salt (Control). On the scale, a 4.0 ml interfacereading was considered to be essentially complete separation.

As shown in FIG. 1, Composition #1 provided faster and more completephase separation compared to the Control, which did not contain aquaternary organopolysiloxane salt. Also, the rate and completeness ofthe separation improved with increased dosage of the quaternaryorganopolysiloxane salt.

FIG. 2 is a graph of the phase separation as a function of total elapsedcentrifuging time for a S. Spinosa fermentation broth using di-isobutylketone as extraction solvent, and demulsifying compositions containing aquaternary organopolysiloxane salt and a quaternary epihalohydrinpolyamine copolymer, according to Table 2. A demulsifier dosage of 2,000μl demulsifier composition per liter of broth was used in these tests.

As shown in FIG. 2, Compositions #4, 5, & 6, provided faster and morecomplete phase separation compared to the similar Control and to thebroth treated with Composition #2 which did not contain a quaternaryorganopolysiloxane salt.

Example 2

The phase separation of a S. Spinosa fermentation broth with di-isobutylketone as extraction solvent was evaluated using the same proceduredescribed in Example 1. Demulsifying compositions of the presentinvention including a mixture or blend of KR-DP0320 quaternaryorganopolysiloxane salt, with KR-C1620 quaternaryepihalohydrin/polyamine copolymer composition. The interface levelsafter 1 minute of centrifugation for various blend ratios are compiledin Table 3 and FIG. 3. The compositions containing a quaternaryorganopolysiloxane salt demonstrated a faster separation rate andimproved completeness of phase separation. The quaternary epihalohydrinpolyamine alone exhibited limited demulsification performance on the S.Spinosa broth, whereas addition of the quaternary organopolysiloxanesalt markedly improved the separation efficiency of the demulsifier.

TABLE 3 Demulsifier composition Interface Level (ml) KR-DP0320 KR-C1630Dosage = 4083 μl of demulsifier (wt %) (wt %) composition per liter ofbroth 0 100 7.5 10 90 6.4 20 80 6.2 30 70 4.9 40 60 4.2 50 50 4.0 60 403.9 70 30 4.0 80 20 4.2 90 10 4.1 100 0 4.1

Example 3

The phase separation of a S. Spinosa fermentation broth with di-isobutylketone as extraction solvent was evaluated using the same proceduredescribed in Example 1. Demulsifying compositions of the presentinvention included a mixture or blend of a quaternary organopolysiloxanesalt with either a quaternary epihalohydrin polyamine or a p(DADMAC).The interface levels after 1 minute of centrifugation for various blendratios are compiled in Table 4. The compositions containing a quaternaryorganopolysiloxane salt demonstrated a faster separation rate andimproved completeness of phase separation. Either a quaternaryepihalohydrin polyamine or a p(DADMAC) alone exhibited limiteddemulsification performance on the S. Spinosa broth, whereas addition ofa quaternary organopolysiloxane salt markedly improved the separationefficiency of the demulsifier.

TABLE 4 Dosage in μl of Demulsifier Composition per liter of brothDemulsifier 2000 4083 6258 8534 Composition Interface Level (ml) #2 7.17.5 7.1 6.6 #3 7.1 8.3 7.6 7.7 #5 4.9 4.0 3.8 — #7 5.9 3.9 3.9 — #1 4.74.1 4.0 4.0

Example 4

The phase separation of a S. Spinosa fermentation broth with di-isobutylketone as extraction solvent was evaluated using the same proceduredescribed in Example 1. Demulsifying compositions of the presentinvention included a blend of KR-DP0356, a quaternary organopolysiloxanesalt, with, KR-C1630, a quaternary epihalohydrin polyamine copolymer.Propylene glycol and water were the carrier solvents for thedemulsifying composition. The interface level after 1 minute and 5minutes of centrifugation, respectively, for various treatment rates iscompiled in Table 6. The composition components and amounts are as setforth in Tables 5 and 6 below.

TABLE 5 Composition # (wt. %) Component #1 (wt. %) Component #2 8 20KR-DP0356 80 KR-C1630

TABLE 6 Composition #8 Dosage (μl of demulsifier composition per literInterface Level (ml) Interface Level (ml) of broth) after 1 minute after5 minutes 500 9.4 7.2 1,021 8.9 7.2 1,565 7.5 6.2 2,134 6.7 5.3 2,7306.0 4.8 3,357 5.7 4.6 4,612 4.4 4.3 5,866 4.2 4.1

As shown in Table 6, varying amounts of a fixed blend of quaternaryorganopolysiloxane salt and quaternary epihalohydrin/polyamine copolymeraccording to the present invention provided good phase separation. Asthe dosage was increased, the rate of phase separation increased and thecompleteness of phase separation improved.

Example 5

The phase separation of a Saccharomyces cerevisiae fermentationbio-broth using toluene as the extraction solvent was evaluated. Thisbio-broth was mixed with toluene at a ratio of 1 part broth to 1 partsolvent. The demulsifying composition of the present invention containedKR-DP0320 quaternary organopolysiloxane salt and a carrier solvent,hexylene glycol. The amount of demulsifier added to the bio-broth was4,830 μl of demulsifier composition per liter of broth. The bio-brothwas separated using the same procedure as in Example 1 above. Theresults are as set forth in Table 7 below. On the scale, 5.0 ml phaseseparation was considered to be essentially complete separation.

TABLE 7 Interface Level (ml) after Specified Centrifuge Time KR-DP03204830 μl of demulsifier composition Time Control per liter of broth 0.5minutes 10.0 5.1 1.0 minutes 8.1 5.0 2.0 minutes 7.2 4.95 5.0 minutes6.3 4.95

As shown in Table 6, the quaternary organopolysiloxane salt provided asignificantly enhanced rate of separation and a higher degree ofseparation when compared to the untreated Control.

Example 6

The phase separation of a bio-broth consisting of a beef extract withpeptones using toluene as the extraction solvent was evaluated. Thebio-broth was a biologically based material with a very high proteincontent which acts as an emulsion stabilizer in aqueous/organic systems.The concentration of the broth was approximately 10% beef extract andpeptones by weight with the remaining being de-ionized water. Thisbio-broth was mixed with toluene solvent at a ratio of 13 parts broth to20 parts toluene. A demulsifying composition of the present inventioncontaining KR-DP0320 quaternary organopolysiloxane salt and hexyleneglycol carrier solvent, was added at a dosage rate of 3,000 microlitersof quaternary organopolysiloxane salt composition per liter ofbio-broth. The bio-broth was separated using the same procedure as inExample 1 above, except that the demulsifier and amount is as set forthin Table 8 below. On the scale, 3.8 ml phase separation was consideredto be essentially complete separation.

TABLE 8 Interface Level (ml) after Specified Centrifuge Time KR-DP0320Control 3,000 μl of demulsifier composition Time (No Demulsifier) perliter of bio-broth 0.5 minutes 9.8 3.8 1.0 minutes 9.5 3.8 2.0 minutes9.1 3.8 5.0 minutes 6.6 3.8

As shown in Table 8, the presence of a quaternary organopolysiloxanesalt provided a significantly enhanced rate of separation and a higherdegree of separation when compared to the untreated Control.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof. It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications which are within the spirit and scopeof the invention, as defined by the appended claims.

What is claimed is:
 1. A method for demulsifying an emulsion comprisingan aqueous phase and an organic phase, comprising (a) adding aneffective amount of a composition to an emulsion comprising an aqueousphase and an organic phase to at least partially separate the aqueousphase from the organic phase, the composition comprising at least onequaternary organopolysiloxane or salt thereof, wherein the quaternaryorganopolysiloxane or salt thereof is represented by Formulae (I) or(II):(R—O)—CH₂CH(OH)CH₂—R′  (I)(R—O)—C(O)CH₂—R′  (II) wherein R is

wherein A is selected from the group consisting of: a bond,—(CH₂CH₂O)_(x)—, —(CH₂CH(CH₃)O)_(y)—, and combinations thereof; a is aninteger from 0 to 200; b is an integer, from 0 to 200; c is an integerfrom 1 to 200; each R¹, if present, is selected from —(CH₂)_(n)CH₃ andphenyl wherein n is an integer from 0 to 10; each R², if present, is—(CH₂)₃—(OCH₂CH₂)_(x)—(OCH₂CH(CH₃))_(y)—(OCH₂CH₂)_(z)—OH; R′ is selectedfrom:

wherein R³, R⁴, and R⁵ are each independently alkyl having from 1 to 20carbon atoms, and X is an ion selected from the group consisting of Cl,Br, CH₃SO₄ and CH₃CH₂SO₄;

wherein R⁶ is alkyl having from 6 to 20 carbon atoms; R⁷ and R⁸ areindependently selected from the group consisting of methyl and ethyl;and n′ is an integer from 1 to 5, and X is an ion selected from thegroup consisting of Cl, Br, CH₃SO₄ and CH₃CH₂SO₄; and

wherein R⁹ is alkyl having from 6 to 20 carbon atoms; and v is aninteger from 1 to 5, and X is an ion selected from the group consistingof Cl, Br, CH₃SO₄ and CH₃CH₂SO₄; and each x, y and z are independentlyselected integers each ranging from 0 to 20, wherein the emulsioncomprises one or more components selected from the group consisting ofbioproducts, microorganisms, enzymes, proteins, lipids, vitamins,carbohydrates, fats, amino acids and mixtures thereof, wherein theemulsion is the product of biological or bioproduct fermentation andwherein the organic phase comprises at least one organic solvent.
 2. Themethod according to claim 1, further comprising (b) allowing the aqueousphase and organic phase to separate into layers after (a).
 3. The methodaccording to claim 2, further comprising (c) removing the aqueous phaselayer from the organic phase layer after (b).
 4. The method according toclaim 1, wherein the emulsion comprises microorganisms or enzymes. 5.The method according to claim 1, wherein the organic solvent is anorganic extraction solvent.
 6. The method according to claim 1, whereinthe organic solvent is selected from the group consisting of amylacetate, methyl ethyl ketone, methyl isobutyl ketone, amyl alcohol,butyl alcohol, toluene, heptane, benzyl alcohol, di-isobutyl ketone,benzenes, xylenes, naphtha, napthalenes, and mixtures thereof.
 7. Themethod according to claim 1, wherein the quaternary organopolysiloxaneor salt thereof is represented by Formulae (I) or (II), wherein R is

wherein x, y and z are integers and are each independently selected from0 to 20, and a, b, c, R¹ and R² are as set forth in claim
 1. 8. Themethod according to claim 1, wherein the quaternary organopolysiloxaneor salt thereof is prepared by reaction of a hydroxyl containingsilicone polymer with a halohydrin or halo acid.
 9. The method accordingto claim 1, wherein the quaternary organopolysiloxane or salt thereof isrepresented by Formula (IIIa):

wherein a and c are as set forth in claim 1, and R is an alkyl grouphaving 1 to 24 carbon atoms.
 10. The method according to claim 1,wherein the quaternary organopolysiloxane or salt thereof is representedby Formula (V):

wherein R is an alkyl group having from 4 to 22 carbon atoms.
 11. Themethod according to claim 1, wherein the quaternary organopolysiloxaneor salt thereof is at least partially water soluble.
 12. The methodaccording to claim 1, wherein the composition further comprises at leastone quaternary epihalohydrin/polyamine copolymer, salt thereof, or(poly)diallyldimethylammonium halide, which comprises up to about 95weight percent of the composition based upon the weight of (1)quaternary organopolysiloxane(s) or salt(s) and (2) quaternaryepihalohydrin/polyamine copolymers or salts, and(poly)diallyldimethylammonium halides in the composition.
 13. The methodaccording to claim 1, wherein the composition further comprises at leastone quaternary epihalohydrin/polyamine copolymer, salt thereof, or(poly)diallyldimethylammonium halide, which comprises about 5 to about95 weight percent based upon the weight of (1) quaternaryorganopolysiloxane(s) or salt(s) and (2) quaternaryepihalohydrin/polyamine copolymers or salts, and(poly)diallyldimethylammonium halides in the composition.
 14. The methodaccording to claim 12, wherein the quaternary organopolysiloxane or saltthereof is added with at least one carrier solvent.
 15. The methodaccording to claim 14, wherein the carrier solvent is selected from thegroup consisting of ethylene glycol, propylene glycol, hexylene glycol,diethylene glycol, polyethylene glycol, polypropylene glycol, glycerol,methanol, ethanol, isopropyl alcohol and mixtures thereof.
 16. Themethod according to claim 1, wherein the effective amount of quaternaryorganopolysiloxane or salt added to the emulsion is about 1 to about200,000 ppm based upon the total weight of the emulsion.
 17. The methodaccording to claim 1, wherein the composition further comprises at leastone quaternary epihalohydrin/polyamine polymer or salt thereof.
 18. Themethod according to claim 17, wherein the epihalohydrin/polyaminepolymer is prepared by the polymerization of at least one epihalohydrin,at least one alkylene diamine and at least one alkylene polyamine inwhich at least some of the nitrogen atoms of the copolymer arequaternized.
 19. The method according to claim 17, wherein thequaternary epihalohydrin/polyamine polymer comprises repeating units:

wherein R and R² are each independently selected from alkyl groupshaving 1 to 3 carbon atoms; E is the residue obtained after bifunctionalreaction of a compound selected from the group consisting ofepihalohydrins, diepoxides, precursors thereof and mixtures thereof; andA is the residue obtained after reaction of a polyfunctional polyamineselected from the group consisting of ammonia, primary amines, alkylenediamines of 2 to 6 carbon atoms, polyalkylpolyamines of the structure:

wherein y represents an integer of about 1 to 5, R₃ is an alkyleneradical of about 2 to 6 carbon atoms, and R₄ is selected from the groupconsisting of hydrogen, alkyl of about 1 to 3 carbon atoms, andω-aminoalkyls of about 2 to 6 carbon atoms, a polyglycolamines havingthe structure:

wherein x is an integer of about 1 to 5; piperazine heteroaryl diaminesor aryl diamines; X⁻ is an ion forming the anionic portion of thepolyquaternary compound, the ratio of m to p being from 99:1 to 85:15; nbeing substantially equal to the sum of m and p; and z is an integerwhich satisfies the anion requirements of the polyquaternary compound.20. The method according to claim 17, wherein the quaternaryepihalohydrin/polyamine polymer and salts thereof comprises repeatingunits:

wherein each of R¹, R², R³ and R⁴ are independently selected fromhydrogen or

and wherein x ranges from about 50 to about 200, y ranges from 0 toabout 10 and z ranges from about 50 to about
 200. 21. The methodaccording to claim 17, wherein the quaternary epihalohydrin/polyaminepolymer or salt thereof is a quaternary fatty epihalohydrin/polyaminepolymer or salt thereof.
 22. The method according to claim 1, whereinthe composition further comprises at least one(poly)diallyldimethylammonium halide.
 23. The method according to claim1, wherein the composition further comprises at least one additiveselected from the group consisting of demulsifiers different from thecationic quaternary organopolysiloxane, non-ionic polysiloxanes,surfactants, wetting agents, compatibilizers and coupling agents. 24.The method according to claim 1, wherein the emulsion further comprisesat least one organic extraction solvent.
 25. The method according toclaim 24, wherein the organic extraction solvent is selected from thegroup consisting of amyl acetate, methyl ethyl ketone, methyl isobutylketone, amyl alcohol, butyl alcohol, toluene, heptane, benzyl alcohol,di-isobutyl ketone, benzenes, xylenes, naphtha, napthalenes, methanol,and mixtures thereof.
 26. A method for demulsifying an emulsioncomprising an aqueous phase and an organic phase, comprising (a) addingan effective amount of a composition to an emulsion comprising anaqueous phase and an organic phase to at least partially separate theaqueous phase from the organic phase, the composition comprising atleast one quaternary organopolysiloxane or salt thereof, wherein thequaternary organopolysiloxane or salt thereof is represented by Formulae(III) or (IV):

wherein in Formula (III): a is an integer from 0 to 200; b is an integerfrom 0 to 200; c is an integer from 1 to 200; and R is an alkyl grouphaving 1 to 24 carbon atoms,

wherein in Formula (IV): a is an integer from 0 to 200; and A isselected from the group consisting of: a bond, —(CH₂CH₂O)_(x)—,—(CH₂CH(CH₃)O)_(y)—, and combinations thereof; and R′ is selected from:

wherein R³, R⁴, and R⁵ are each independently alkyl having from 1 to 20carbon atoms, and X is an ion selected from the group consisting of Cl,Br, CH₃SO₄ and CH₃CH₂SO₄;

wherein R⁶ is alkyl having from 6 to 20 carbon atoms; R⁷ and R⁸ areindependently selected from the group consisting of methyl and ethyl;and n′ is an integer from 1 to 5, and X is an ion selected from thegroup consisting of Cl, Br, CH₃SO₄ and CH₃CH₂SO₄; and

wherein R⁹ is alkyl having from 6 to 20 carbon atoms; and v is aninteger from 1 to 5, and X is an ion selected from the group consistingof Cl, Br, CH₃SO₄ and CH₃CH₂SO₄; and each x, y and z are independentlyselected integers each ranging from 0 to 20, wherein the emulsioncomprises one or more components selected from the group consisting ofbioproducts, microorganisms, enzymes, proteins, lipids, vitamins,carbohydrates, fats, amino acids and mixtures thereof wherein theemulsion is the product of biological or bioproduct fermentation andwherein the organic phase comprises at least one organic solvent.
 27. Amethod for demulsifying an emulsion comprising an aqueous phase and anorganic phase, comprising (a) adding an effective amount of acomposition to an emulsion comprising an aqueous phase and an organicphase to at least partially separate the aqueous phase from the organicphase, the composition comprising at least one quaternaryorganopolysiloxane or salt thereof, wherein the quaternaryorganopolysiloxane or salt thereof is represented by Formula (IVa):

wherein a is an integer from 0 to 200 and R is an alkyl group having 1to 24 carbon atoms and wherein the emulsion comprises one or morecomponents selected from the group consisting of bioproducts,microorganisms, enzymes, proteins, lipids, vitamins, carbohydrates,fats, amino acids and mixtures thereof, wherein the emulsion is theproduct of biological or bioproduct fermentation and wherein the organicphase comprises at least one organic solvent.